Reaction product of aldehydes and triazinyl cyanoalkyl sulphides



' Patented Apr. 27, 1943 Gaetano Drllelio and James Underwood,Pittsfleld, Mass, assignors-to'GeneralElectric Company,a corporation of'NewYork 1 No Drawing. Application June 27,""194 Serial No. 400,149

18 Claims.

This invention relates to the production of new synthetic materials andmore pa'rticularlyto new reaction products ofparticularutllity'in theplastics and coating arts, Specifically theinvention is concernedwithcompositions of matter comprising a condensation product ofingredients comprising an aldehyde, including polymeric aldehydes andaldehyde-addition products, e. g.,

formaldehyde, paraformaldehyde, dimethylol' urea, trimethylol melamine,etc., and a tria'zinyl cyanoalkyl sulphide corresponding to thefollowinggeneral formula: 7

In the above formula 11 represents an'integer and is at least 1 and notmore than 3, a: is an integer and is at least l and not morethan 2, andR represents a member of the classconsisting of (HEN) hydrogen andmonovalent hydrocarbon and halohydrocarbon radicals, numerous examplesof which hereafter are given. Since]: represents an integer which is lor 2, it will be seen that the linkage of the cyanoalkylgroup to thesulphur atom in all cases will be alpha or beta to the cyano group. Italso will be observed that linkage of the triazinyl grouping to'thesulphur atom isthrough a carbon atomfi From a con- .si deration ofthe formula it further wilhbeseen that when'n is 3 there will benoamin'o -NHR) groups attachedt'o the triazine nucleusfilnstead of thes-triazinyl cyanoalkyl sulphides repre sented' by the above formula,correspondingderivatives of the asymmetric triazines "or of the vicinaltriazinesmay beused.

Illustrative examples of monovale nt hydro-j carbon radicals that 'Rinth'e above formula may represent are aliphatic -'(e.' gig-methyl,ethyl, propyL' isopropyl, allyl, 'butyl, secondary's bu'tyl,

isobutyl, butenyL'amyl, isoamyl, .hexyl, etc.) ,ineludingc'ycloaliphatic; (e. g., cyc1opentyl,,cyclo-;

pentenyl, cyclohexyl, cyclohexenyl, cycloheptyl', etc;)-;. aryl (e.'g.,- phenyl, -diphenyl,-: naphthyl', 1 'etc.); 'alkaryl. (e g., tolyl,xylyl, ethylphenyl,

propylphenyl, isopropylphenyl; etc); aralkyl e. g., benzyl, phenylethyl,phenylpropyl, etc.)

and their homologues, aswell as those groups with one or "more oftheirhydrogen atomssubsttuted by, for eigample, .a halogen. examples ofhalogeno-substituted hydrocarbon radicals are chlormethyl,chlorcyclohexyl, chlor;

phenyl, dichlorphenyl, ethyl chlorphenyl, phenyl (01.2 042) i, t o,

"chlorethyl; bromethyl, bromtolyl, etc.- Preferably Rishydrogen; I

' More specific examples of triazlnyl cyanoalkyl *sulphides'that'may beemployed in producing our 7 new condensation products 'are s-triazinyltri- (cyanomethyl sulphide, s-triazinyl tri-(cyanoethyl sulphide), themonoamino (-NI-IR) s-tri- 7' azinyl di-'(cyanomethylsulphides), themonoamino (-NHR) s triazinyl di-(cyanoethyl sulilbf phides); the diaminoIE('--NHR)2] s-triazinyl 'mono-(cyanomethyl sulphides) and the diaminophides) The triazinyl cyanoalkyl sulphides that are l5 used in carryingthe present inventionfinto efiect are more fully described and arespecifically claimed in our copendingapplicationSerial-No. 400,150,filed concurrently herewith; now Patent 'No. 2,295,561, issued September151942, and assigned tothe same assignee as the present invention; l wOther and more specific examples of triazinyl cyanoalkyl'sulphidesthatmay bezusediin pro- 7 ducing our newcondensation productsare listed below: V v

si-Triazinyl-2,4,6 tri -(beta-cyanoethYl sulphide) ,6amin os-triazinyl-2, 1' 'dl-(cyanomethylfsul- Jp v o S-amino s-triazinyl.Z-beta cyanQethyl l-cyar omethyl disulphide l-aniline. ,fi-rmethylamino.s triazinyl -z cam s methyl sulphide phide r fil-amino 4-anilin'o's-triaZ1nyl-2 cyano phenylzmethyl sulphide V cyanoethyl sulphide v7phide' v V 4 cyclohexyl 'cyanobutyl) sulphide 4,6-di-t0'l acyanop'ropyl) sulphide" Y J 4;6-di-(cyclohekylamino) 1 'cyanopropylsulphide cyanopropyl sulphide) s q-ethylamino Sama ium-2,4 n-kwamwmoi Iphen'y'lmethyl'sulphide) I V o s-Triazinyl- 2,4,6 tri-' [beta-(alpha-'phenyl' cyano butyl) sulphide] p li -amino 14 aniline s-. triazinyl-2 I cyanomethyl suli ltd-diamino s-triazinyl-2 alphac'yanoethylsul-V I 4,6-di-(m'ethyl rhino) s-triazinyl-2"beta ialpha idos-triazinylfz beta -(gamma-phenyl cation Serial No. 400,150.

The present invention is based on our discovery that new and valuablematerials of particular utility in the plastics and coating arts can beproduced by eifecting reaction between, ingredients comprisingessentially an aldehyde, including polymeric aldehydes andaldehyde-addition products, and certain triazinyl cyanoalkyl sulphides,numerous examples of which have been givenabove and in ourabove-identified copending application. j

Resins heretoforehavebeen made by condensing an aldehyde with certainthioammellne ethers, but such known resins are not entirely satisfactoryfrom the standpoint of optimum heat waterand abrasion-resistance and incuring characteristics. One possible explanation for these deficienciesin desirable properties is the fact that the starting material containsthio etc. Mixtures of acids, of acid salts or of acids and of acid saltsmay be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the triazinederivative used in practicing our invention may be carried out in thepresence of solvents or diluents, fillers, other naturalor syntheticresinous bodies, or while admixed with. other-materials which also canreact with the aldehydic reactant or with the triazine derivative, e.g., ketones, urea, thiourea,

s elenourea, iminourea, (guanidine), substituted ureas, thioureas,selenoureas and iminoureas, nu-

merous examples of which are given in various copending applications ofone of us (Gaetano F.

DAlelio) for instance, in DAlelio copending application Serial No.363,037 filed October 26, 1940; monoamides of monocarboxylic andpolycarboxylic acids and polyamides of polycarboxylic groups that arealdehyde-non-reactable. In

marked contrast the starting organic sulphides usedrin practicing thisinvention contain alde- ,hyde-reactable nitrilo-thio groups attached toV the triazine nucleus, thereby imparting to the. condensation productsof such sulphides with aldehydes increased heat-, waterandabrasionresistance and improved curing characteristics as compared withknown resinous condensation products of an aldehyde and a thioammelineether.

In practicing our invention the initial condensation reaction may becarried out at normal or at elevated temperatures, at atmospheric,subatmospheric or super-atmospheric pressures and kaline or acidconditionsfor theinitial conden sation reaction. For example, we may usean alkaline substance such as sodium, potassium or calciumhydroxides,sodium or potassium carbonates, mono-, dior tri-amines, etc. Good re- 7sultsare obtained by causing the condensation reaction between theprimary components to take place in the presence of a primarycondensation catalystand a secondary condensation catalystfCondensationproducts of excellent timeor storage-stabilitycharacteristics areobtained byfusing as the primary catalyst a'member'oithe class consisting'of (1) nitrogen-containing basic tertiary compoundsthat are aldehyde-non-reactable, e. g., tertiary amines such astrialkyl'ie. g.,

trimethyl, triethyl, etc.) amines, triaryl (e. g.-,

- ing applications, foriinstance, in DAlelio copending applicationSerial No.1 377,524, filed Feb. 5,

acids, e, g., acetamide, halogenated acetamides, 'e.; g.,' a chlorinatedacetamide, maleic monoamide, malonic monoamide, phthalic monoamide,maleic diamide, furnaric diamide, malonic diamide, itaconic diamide,succinic diamide,

phthalic diamide, the monoamide, diamide and,

1941, and in applicationsrreferred to in said copending application;aminodiazines and aminocohol, ethylene glycol, 'glycerine, polyvinylalcohol, etc.; amines, including aromatic amines,

pending application Serial No. 363,037 with particular reference. to.reactions involving a urea,

an aldehyde and a semi-amide of oxalic acid.

7 For instance,we;ma'yform a partial condensatriphenyl, 'tricresyl,etc.) amines, etc.,and'(2) nitrogen-containing basic compounds'that arealdehyde-reactable, for instance ammonia, pri- J mary aminesie. g.,ethyl amine, propyl amine,

etc.) and secondary amines (e. g, v,dipropyl amine, dibutyl amine, etc).The secondary condensation. catalyst, which ordinarily is used in anamount less than the amount ofthe primary cat alyst, should'be a fixedalkali, forinstan ce, a carbonate, cyanide or hydroxide of analkali'metal (e, g., sodium, potassium, lithium, etc).

Illustrative examples of acid condensation catalysts that may beemployed are inorganic'or orphosphoric, acetic, lactic, acrylic,malonic, letc., ofr acid salts vsuch -as sodium acid sulphate,

monosodium'phosphate, monosodium phthalate,

tion product of ingredients comprising urea, a dlaminotriazinylcyanomethyl sulphide andformaldehyde and thereafter eifectreactionibetween this partialfcondensation product and, .for example,aschlorinated acetamide toobtain' a heat-- curable composition. v V

Some of the condensation roductsof this inventionarethermoplastic-materials even at an.

advanced stage of;- condensation while. others are j thermosetting j orpotentially thermosettingare particularly useful in"producing moldingcompounds suitable for use in making pieces to 5 be molded over'screws(as in making-bottle caps).

ganie acids such as hydrochloric, Sulp u i i I jmixed with fillers,pigments, dyes, lubricants,-

V plasticizers, etc.,' may be used, for example,in the 7a Thethermoplastic condensation products are of particular utility asplasticizers for other synthetic resins. The. thermosetting orpotentially f 7 thermosetting condensation products, alone or productionoi molding compositions- Aqueous formaldehyde The heat-curable resinouscondensation products of this invention show good flow characteristicsduring a short curing cycle. This is a. property that is particularlydesirable in a molding compound. The molded resins are of exceptionallylight color. Products of any desired colors can be obtained byincorporating 'a suitable pigment into the molding compound. The

molded articles have good surface finish and ex-. cellent resistance towater and arcing. They have a high dielectric strength; The pH at whichthe heat-curable resins of this invention cure generally is of the orderof 5.0 to 8.0. Basic fillei's such as asbestos, therefore. can be usedsatisfactorily in the production of molding compounds,

surface finish and showed good. flow character-,

istics during molding.

Instead of employing sulphamic acidpas above" described in acceleratingthe curing of the potentially reactive resinous materiaLheat-convertible7 compositions may be produced by adding 'tothe syrup direct or activecuring-catalystszie. g.,

phthalic anhydride; citric acid, etc.), or latent curing catalysts (e.g., sodium: chloracetate;

N-diethyl: chloracetamide, glycine. ethyl: ester hydrochloride, etc.) orby-intercondensation with p V 7 other curing reactants (e. g.,.mono-,diand'triwithout detrimental efiect upon the rapidity of cure of thecompound.

Depending upon the particular reactants em-' ployed and the particularconditions of reaction,

7 volatile solvents to form liquid coating composttions of adjustedviscosity and concentrations. The heat-convertible or potentiallyheat-convertible resinous condensation products may be used in liquidstate, for-instance, as surface-coating materials, in the production ofpaints, varnishes, lacquers, enamels, 'etc., for general adhesiveapplications, in producing laminated articles and for numerous otherpurposes. The liquid, heat-hardenable or potentially heat-hardenablecondensationproducts also may be .used directly as casting resins, whilethose which are of a gel-like nature in partially condensed state may bdried and granulated tof orm' clear, unfilled heat-convertible resins.

Inorder that those skilled in the art better may understand how thisinvention maybe carried into efiect, the 'iollowing examples-are givenby wayof illustration. All parts are by weights 3 Example 1 4,6-diaminos-triazinyl-Z cyanomethyl sulchloracetamides, chloracetonitriles, alpha,betadibrompropionitrlle, aminoacetamide hydrochlo ride,aminoacetonitrile hydrochloride, ethylene diamine mono-hydrochloride,-diethanol amine hydrochloride, nitrourea, glycine, chloracetyl urea,chlora'cetone, citricdiamide; 'phjenacyl chloride, etc.). Other examplesof active and latent curing catalysts and of curing'reactants that maybe employed toaccelerate or to effectthe curing of the thermosetting or"potentially thermosetting resins of this and other examples are given invarious DAlelio copendingapplications, for instance, in copendingapplication Serial No. 346,962, filed July 23, 1940, and Serial No.354,395, filed August 27, 1940, both of which applications are assignedto the same assignee as the present invention.

Example 2 Parts 4,6-diamino s-triaZinyI-Zcyanomethyl sulphide a 72.1,Urea e-; ,108.0 Aqueous formaldehyde ap rox. 37. 1% HCHO) 7 324. Sodiumhydroxide in -15- parts water 0.3

were heated together under reflux for 30. minphide 72-8 (approx. 37.1%

O 7 Sodium hydroxide in 10 parts water..

to a solid resin having a very high fusion point.

The addition of a small amount (0.5 m)- 01 sulphamic acid to 115 partsof the resinous syrup,

followed by refluxing for an additional 5 minutes to cause the sulphamicacid to intercondense with the partial condensation product'- of.

the triazlne derivative andiormaldehyda'prm' duced a resin thatcuredrapidly to an'insoluble,

iniusible state. A molding (moldable) compound was prepared bymixing'this resinous syrup with 35 parts alpha cellulose in flock formand 0.2

part of V a mold lubricant, speciflcally zinc stearate. The wet compoundwas .dried.-'at 7 5- C.

for 1 hour. A- sample of the dried compound was molded for 5 minutes at130? C. under a pressure or 2,000 pounds per, square inch. The moldedarticle was well-curedthroughout, had a glossy -utes,;.yielding. aresinous syrup that bodied to a thermoplastic resin when. a sample wastested ona140f C. hot plate. A heat-curable resin,is produced byincorporatinginto thesyrupy solu;-; tion or into the solid'resin activeorlatent curing catalysts, or by intercondensati0n ;with curingreactants as described. underrExample Five-tenths (0.5)qpartsulphamidacid was added to 230 parts of theabove syrup and :the'mixture was heated under refiuxfor two minutes; The resulting hot syrupwas mixed with parts alpha flock and 0.4 part zinc stearate to form amolding compound. The wet compoundjwasgg dried at Qror; two hours.';;Awell-cured? moldedpiece was produced by moldingasample j of the driedcompound for-5 minutes atl30 C under a pressure of 2,00o poundspersquare inch.-

r riampze 3' T i f f 604,6-diamino s,- -triazinyl.-2 cyanomethyl 5Phenol, synthetic;; L; e L; ;;Q Q

heated underreflux for' '45 minutes to cause "the triazinegderivativeto. .react with the phenol-1 formaldehyde". partial condensation;-product; The resulting resinous syrupwas'acidifled by;

adding; parts oxalic: acid dissolved in ;20 parts water. The acidifiedsyrup. cured. to an insoluble, infuslble-state when asmall sample or itwas tested on a 140 C. hotplate. r

, A. molding, compound was prepared by'mixing the acidified syrup. with114 parts alpha cellulose and 1 partzinc stearate. Thewetcompound'wasdried for 3 hours at 75 C. A%well-cured-.molded article, was producedbypressinga sample of; the

were heated together under reflux for 30 minutes. A heat-curable resin.is produced by incorporating into the syrupy mass active or latentcuring catalysts or curing reactants as described-under Example 1. Theresultingproduct is suitable ior use in the production of moldingcompounds.

This resin is especially suitable for use when products of light colorare. oi secondary consideration.

Example 5 v Acetamide dried compound for; 5 minutes at. 130- C. under apressure: of 2,000 poundsperasquare inch. The. molded: piece hadexcellent cohesive properties,- and showed .good flow-characteristicsduring molding. Q

Example-4 t I 7 .Parts 4,6-diamino s-triazinyl-2 cyanomethyl sulphide;18.2' Furfural g 57.6 Sodiumhydroxldein 5 parts-water 0.1 Water- -100:0

7 Sodium hydroxide in 5 parts water 7 Parts 4,6-diamino. s-triazinyl-Zcyanomethyi sulphide Y 18.2 Acrolein 33.6 Sodium hydroxide. in 5partswater 0.1

The above components wereheated together under reflux for 30minutes,yielding a thick resinousf mass. When a sample of this'resin' was heatedon a 140 C. hot plate it cured to an infusible state. A more rapidlycuring resin is produced by the use of, for example, citric acid,glycine or other direct orlatent curing catalysts or curing reactantssuch "as described under Example 1. to attack by water. p

, Example 7 6 4.6-diamino" s-triaz1nyl-2-cyanomethyl s were heatedtogethenunder reflux for minutes, yielding a. clear'syrup. When thissyrup 'wasdehy'drated by heating itat 100-120 C.; a viscous resinousmass soluble in. Solvatone' was obtained. A solid resin having aiveryhigh fusion Thecured resin is extremely resistant Parts phide 7 7 v18.2- Butyl alcohol 74.0

Aqueous 'for1naldehyde' (a "rox.-- 37.1%;- V

-HCHO)"** V 81.0 Sodium hydroxide in 10 parts water 0.2

point was produced by heating the dehydrated" resin-furtherat 140' C.A'thermosetting resinous composition isobtained by incorporating into"the syrupysolution; or into the thermoplastic resin, active or latentcuring catalysts or curingv reactants as described'under Exaniple 1. Thesolubilityand film-forming characteristics" of this resin make itespecially suitable foruse in the production ofspirita'nd ibakingvarnishes.

Thus'itmay be 'used, Iorexampla-as a-rnodifier o1 varnishes. of ;theaminoplast and alkyd-resin Example 7.

'- a Parts 4,6-diamino s-triazinyl-2 cyanomethyl. sulphide.

Diethyl maionate 16.0

Aqueous. formaldehyde (approx. 37.1%

HCHO) 64.8

Sodium hydroxide in 5 parts water 0.1

were heated together under reflux for 30 minutes, yielding a' thicksyrupyresinous mass. The addition of active or latent curing catalystsor curing reactants as describedunder Example 1 yields a heat-curableresinous composition. The unmodified, uncured resin was found to beinsoluble in waterand in in Solvatone.

Example 8 Parts 4,6'-diamino s-triaz'inyl-Z cyanomethyl sulphide 18.25.9

Aqueous formaldehyde (approx. 37.1%

. HCHO) I 56.7

were heated together under reflux for 30 minutes, yielding a syrupymassthat was converted into athermoplastic resin when dehydrated at C. Aheat-hardenable resin is produced by incorporating active or latentcuring catalysts or curing reactants, such as described under Example 1.either into the syrupy solution or into the thermoplastic resin- 7Example 9 Parts 4,6-diamino s-triazinyl-2 cyanomethyl sulphide' -1 18.2Glycerine Aqueous formaldehyde. (approx. 37.1% p HCHO) Q 64.8Sodiumhydroxide infi'parts water 0.1

The above. components were heated together under reflux for 30 minutesto yield a clear syrup that bodied to tit-thermoplastic resin whendehydrated at 140 C. Heat-curable products are obcuring characteristics.

Example 10 4,-6-diamino s-triazinyl-2 cyanomethyl sulfphide 18.2Polyvinyl alcohol 1 26.4 Aqueous formaldehyde (approx. 37.1%

HCHO) 97.2 1 Sodiumhydroxide in 5 parts water 0.1 Water 200.0

were heated together under reflux for 30 minutes. The resulting syrupymass formed a thermoelastic film when a smallqsample of it was heatedona 140 C. hot plate. This syrup is suitable for use in the manufactureor baking varnishes. When a sampleot the syrup was alcohols butwas'soluble Parts treated with a curing agent, specifically asmallamount of hydrochloric acid, and the resulting product baked in filmform on a glass surface for severalhours at 75-80 C.. a baked film thatwas transparent, tough and not attacked by water was obtained. Theresinous composition of this example also may be usedin the preparationof molding compounds after incorporating 1 formaldehyde or compoundsengendering formaldehyde, e. g., paraformaldehyde,hexamethylenetetramine, etc. Illustrative examples of other aidehydes that may beused are acetaldehyde, propionaldehyde, butyraldehyde, methacrolein,crotonaldelzg de', benzaldehyde, furfural, etc., mixtures thereof, ormixtures of formaldehyde (or compounds engendering formaldehyde) withsuchaldehydes. Illustrative examples of aldehyde-addition products thatmay be used instead of the aldehydes themselves are the mono-fendpoly-(N-carbinol) derivatives, more particularly the monoandpoly-methylol derivatives, of urea, thiourea', selenourea and iminourea,and of substituted ureas, thioureas, selenoureas and iminoureas'(numerous examples of which are given in DAlelio copending applicationSerial No. 3'77,524, monoand poly-(N-carbinol) derivatives of amides ofpolycarboxylic acids, e. g maleic, itaconic,j fumari'c, adipic, malonic,succinic, citric, phthalic, etc., monoand poly- (N-carbinoD- derivativesof amidogentriazines,

numerous examples of which are given in DAlelio copending applicationSerial No. 377,524. Barticularly good results are obtained with activemethylene-containing bodies such as monoand di-methylol ureas and themethylol melamines, e. g., mono-', di-, 'tri-, tetra}, pentaandhexamethylol melamines. Mixtures of aldelwdes-and aldehyde-additionproducts may be "employed, e. g., mixtures of formaldehyde and methylolcompounds such, for instance, as dimethylolurea andtrimethylol melamine.

The ratio ofthe aldehydic reactant to the triazine derivative .may bevaried over a wide range, but ordinarily the reactants are employed inan amount corresponding-to at least one mol of the aldehyde,specifically formaldehyde, for each mol of the'triazine derivative. Thuswe may use, for example, from oneto five or six mols of an aldehyde foreach mol of triazine derivative. When the aldehyde is available forreaction in the form-of analkylol derivative,

instance, as dimethylol urea,trimethylol melamine, etc., then higheramounts of such aldehyde-addition products ordinarily are used, forexample, up to or 12 mols of suchalkylol derivatives for each mol of thetriazine derivative.

As indicated herelnbefore, and as further shown by a number of theexamples, the properties of the fundamental resins of this invention maybe varied widely by introducing other modifying bodies before, during orafter effecting condensation between the primary components. Thus, asmodifying agents-we may use, for instance, monohydric alcohols such asethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols; polvhydricalcohols such as diethylene glycol,

of high molecular weight bodies with or Jwithout v v mention-salts-of (1triazine, derivatives of;t he

more particularly a methylol derivative such, for

um, chloracetonitrlles, etc. ;v and others.

.or unsaturated polyhydric a1coholpolycarboxylic gvinyl butyrate, etc.,polyvinyl ethers including 1 r polyvinyl acet'als,v specificallypolyvinyl formal, I

.phuric, phosphoric, .bo'ric, acetic, -chloracetic,

triethylene sl -(=01, pentaerytbritol, etc. amides such as. formaniide,stearamidal-facrylamide, benzamide, toluene sulphonamides, benzenedlsulphonamides, benzenetrisulphonamidespadipitz diamide, phthalamide,etc.; aminessuchFas' ethylene diamine, phenylene diamine, etci; phenolandsubstituted phenols, including amino; phenols, etc.,; ketones,including halogenated ketones; nitriles, including halogenated nitriles.

e. g .acrylonitrile, methacrylonitr'ile, -succinoni- The modifyingbodies also may take theform resinous characteristics, for example,hydrolysed wood products, formalized cellulose derivatives, lignin,protein-aldehyde condensation products, resinous 7 reaction products ofaldehydes for example formaldehyde, with the aminotria zoles (e.g.,guanaz ole, phenyl guanazole, etc.), a loue or admixed with, forexample, urea, me1a mine, or

urea and melamine, resinsobta'inedby reaction of an aldehyde with th eaminodiazines -'(e. g., 2,4,6-triaminopyrimidine,gA diaminoquinazoline,etc.), or with aminotriaaines other thanthose with which this. inventionis concerned, orwith the aminodiazoles, alone or admixed with, forexample urea, melamine or urea and melamin el 1 Other examples ofmodifying bodies are the ureaaldehyde condensation products, theanilinealdehyde condensation products, furfural conf densation products,phenol-aldehydecondensael I 1 tion products, modified orunmodified-saturated acid condensation products, watersoluble cellulosederivatives, natural gums-and resins such as shellac, rosin, etc.;polyvinyl compounds such I I as polyvinyl esters, e.'g., polyvinylacetat polyetc. Instead of effecting reaction between a tri'-" azinylcyanoalkyl sulphide of the'kind herein described and an aldehyde,'e. g.,formaldehyde, we may cause an aldehyde tocondense'with' a salt of thetriazine derivative or with a mixture of the triazine derivativeand. asalt"(orga'nicor inorganic) thereof. As examples of s'altslof the:triazine derivatives :that may be usemlwe class consistingo'iimono'ainino (-'-NHR),,and'dia amino [(NHR),2], fiazinyl cyanoniethyland cyanoethyl sulphides. and (2) organic or yinor ganic acids as, {forinstance, hydrochloriagsul propionic, butyric, valeric,., acrylic,polyacrylic, methacrylic, polymethacrylic, oxalic, malonic,; succinic,adipic, malic, maleic, fumar'ic,;benzoic, salicylic,camphoric,'phthalic, etc. a Dyes, pigments, plasticizers, moldlubricants, :1

opacifiers and various fillers '(e. g., wood flour, 7

glass fibers, asbestos, including defibrated asbes- I tos,mineral wool,mica,'cloth' cuttingsetcJPmay'- f be compounded with the resi'n'inaccordance. with conventional practice'to"provideivarious The modifiedandunmod fied Y j 'l' positions of thisjinvention haye a wide.'-.vii.riety' of uses. For example, in additlonto'their-ilse in theproduction of molding compo m k h i an aldehyde.

may be, used as modifiers of other natural and synthetic resins, aslaminating varnishes in the production of laminated articles whereinsheet materials, e. g., paper. cloth, sheet asbestos, etc., are. coatedand impregnated with the resin, su-

perimposed and thereafter 'united under heat and pressure. They may beused in the pro duction-of wire'or'b'aking enamels, for bonding abrasivearticlessuch, for instance, as grindstones;qsandpapers, etc., in themanufacture of 'ele'ctrical'resistors, etc. I'hey also may be employedfor treating cotton. linen and other cellulosiomaterials in sheet orother form. They also'inay be used as impregnants for electrical coilsand'for other electrically insulating applications.

-What'we claim as new and desire to secure by Letters Patent of theUnited States is:

r *1. A composition ofmatter comprising the reaction" product of 7ingredients comprising an r aldehyde and a triazinyl cyanoalkylsulphidecorresponding to the general'formula where n is an integer andis atleast 1 and not mor'e than 3,- a: is 'an'integer and is at least 1andnot more than 2, and R is a member of the class consisting ofhydrogen and monovalent I hydrocarbon and halo-hydrocarbon radicals.

2. A composition as in claim 1 wherein the aldehyde is formaldehyde. 1 1'3. A composition comprising a condensation product of ingredientscomprising an aldehyde.

and a triazinyl cyanoalkyl sulphide corresponding to the generaliormulawhere n is an integer and is at least 1 and not more than 3; a is aninteger and is at least 1 and not more than'2; and R representshydrogen.

4. A composition comprising a condensation product of ingredientscomprising formaldehyde and a -tria'zinyl 'cyanoalkyl sulphidecorresponding to the general formula 1.

where n is an integer-and is at least 1 and not morethan 3,. Rrepresents hydrogen and a: is 1. 5-.A composition comprising the productof treactionoi' I ingredients comprising symmetrical tria'z'inyl- 2,4.6tri-(cyanomethyl sulphide) and an aldehyde. I

A resinous composition comprising the product of reactionoi' ingredientscomprising a .mono amino. s-triazinyl' (ii-(cyanomethyl sulphide) andanaldehyde. i

v7. Airesinous composition comprising the ,product of reactionofingredients comprising a diaminocs-triazin'yl" cyanomethyl sulphideand *orcementing together mica iiakes to form a laminated mica article,for bonding together abrasive grainsin the production of resin-bondedthe general formula 8. A resinous composition comprising the product .ofreaction of ingredients comprising formaldehyde and 4,6-diamino.s-triazinyl-2 I cyanomethyl sulphide.

9. A heat-curable resinous condensation product of ingredientscomprising formaldehyde and\ a triazinyl cyanoalkyl sulphidecorresponding to where n is an integer and is at least 1 and not morethan 3,. Rfrepresents hydrogen and a: is 1.

10. A product comprising the cured resinous condensation product ofclaim 9.

11. A composition as in claim 1 whereinthe aldehyde.

V 14. A composition comprising the product of 1 reaction of ingredientscomprising melamine, a

diamino s-triazinyl cyanomethyl sulphide and formaldehyde. v

15. A composition comprising the product of reaction of ingredientscomprising-a phenol, an aldehyde and a triazinyl cyanoalkyl sulphidecorresponding to; the general formula (we: I I

where n is an integer and is at least 1 and not .more,than.3, a: is aninteger and is at least 1 and not more than 2, and R is a memberv or theclass consisting of hydrogen and monovalent hydrocarbon' andhalo-hydrocarbon radicals.

16. A heat-curable composition comprising the heat-convertible productof reaction of (1) a partial condensationproduct of ingredientscomprising .urea, a diamino s-triazinylcyanomethyl sulphide andformaldehyde and (2) a chlorinated acetarnide.

17. A product comprising the cured composition of claim 16.

18. The method of preparing new condensation products which compriseseii'ecting reaction between ingredients comprising an aldehyde and atriazinyl cyancalkyl sulphide corresponding .to the general formulawhere n is an integer and is at least 1 and not more than 3, a: isaminteger and is at least 1 and not more than 2, and R is a member ofthe class consisting of hydrogen and monovalent hydrocarbon andhalo-hydrocarbon radicals.

GAETANO F. DALELIO. JAMES W. UNDERWOODL

